Dyeing preparation



Patented Oct. 11, 1932 UNITED STATES PATENT OFFICE JOSE! HALLER, OI wIFSDORF-ON-THE-RHINE, EUGEN GLIETENBERG, OF LEVER- KUSEN -0N-'1HE-BHINE, AND 'WINFRID HENTRICH, OF WIESDORF-ON-THE-RHINE, GERMANY, ASSIGNOBS T0 GENERAL ANILINE WORKS, 0., OF NEW YORK, N. Y A

CORPORATION OF DELAWARE DYEING rBEPABATION No Drawing. Application filed February 12, 1930, Serial No. 427,888, and in Germany February 25, 19229.

The present invention relates to new compositions of matter suitable for dyeing and printing processes.

In accordance with this invention a wateror alkali-soluble composition for dyeing and 5 R meaning an aromatic nucleus free from r a sulfonic or carboxylic acid group, R meaning an aromatic or aliphatic hydrocarbon residue at least once substituted by a sulfonic or a earboxylic acid group anda: mean? ing hydrogen or R are obtainable by diazotizing in the usual manner any primary aromatic amine free from a sulfonic or carboxylic acid group and adding to the diazo solution, preferably at low temperature, the equivalent quantity of a primary aromatic being at least once substituted by a carboxyhc or a sulfonic acid group. The diazo amino compounds separate or, if necessary, are salted out.

As coupling components there may be mentioned by way of example, naphthol,

2.3 hydroxynaphthoic acid Our new compositions are valuable for dyeingand printing; for the production of fast dyeings on the fiber it is only necessary to dissolve these compositions in water or I in water containing alkali, in order to obtain dyestufiprepa'rations ready for use in dyeing and printing. On acidification the diazo amino compound issplit up into the two components, whereupon coupling between the diazo compound and the coupling component present occurs. A further advantage of the compositions described lies in the fact,

that their solutions are very stable, some-of the-same considerably surpassing in this respect similar, hitherto known products. In the attached table some examples of the new compositions of this type are set forth but or secondary aromatic or aliphatic amine, this table is not intended to be exhaustive:

No Base Stabilizer Coupling component Shade 1... 2.5-dichloro-l-amino-benzene 4-su1fo-2-amino benzoic acid Diacetoacetyl-o-tolidide Yellow j 2 2.54iichloro-l-amino-benzene 5-sullo-2-amino benzoic acid 2.1- dichloro-4-nitro-l-aceto-acetylamano- Yellow unzene 3. 4-chloro-2aminc-l-methylbenzene 4-sulfo-2-amino benzoic acid Diacetoacetyl-o-tolidide Yellow 4. 4.5-dichloro-2-amino-l-methylbenzene 4-su1lo-2-amino benzoic acid D acetoacetyl-o-tol d de Yellow 5... 4-chloro-2-amino-l-methoxy benzene Methylamino acetic'acid D acetoaretyl-o-tol d de Yellow 2.5-dichloro-l-methyl-aminobenzene 1-aminobenzene-2.5-disulfonic acid Diacetoacetyl-o-tolidide Yellow 5-nitro-2-amino-l-methy1benzene l-methyl-Z-ethyl-amino-benzene-4- Sodium compound oi 4-n1tro-2.5d1meth-' Yellow sulfonic acid oxy-l-acetoacetylammo benzene 8... 3-chloro-l-aminobenzene 4-sulfo-2-amino benzoic acid 2-hytdil'oxg-1aphthalenaZi-earboxylic acid- Orange 0- 0 [ll 1 e 9.-. 3-ehloro-1-aminobenzene 4 amino 1 methylbenzene 2 Sodium compound ot 2-hydroxy-naphtha- Orange sulfanilide lene-3-carboxy11c acid-o-toluldide I V 10-- 2.5dich1oro-1-aminobenzene 4-sulfo-2-amino benzoicacid 2-h droiyggphthalene-3-carboxylicacld-o- Orange p enei l e a. 11.- 2.5-dichloro-l-aminobenzene 4-su1f0-2-amino benzoic acid Sodium eompoundol Z-hydroxy-naphtha- Orange lene-3-carboxylic acid-o-phenetidide 12.- 4-ch1oro-2-amino-l-methylbenzene 4-sullo-2-amino benzoic acid z-hydgoryg gpihthalene-B-carboiylic acid- Scarlet o-p one 1 e fioo No. Base Stabilizer Coupling component Shade 13-. 2 amino 4 methoxy 6 -benzoyl- 4 mlio 2 methylamino-benwic Shydroxg-naphthalane-d-carboxylic acid- Violet amino-ichlorobenzene 1 ac l i ido I 14.. 2.6-dichloi'o-1-aminobenzene 4-si11io-2-amiiio-benzoic acid Mg gynad phthalene-a-cai-boxylic acid-o- Scarlet a e 16.. 2.5-dicliloro4'amino-1-methylbenzeue b-sulio-Z-amino-banzoic acid Sodium compound of z-hydizfiw-flflphtllfl- Scarlet leno-ii-carboxylic acid-o-anisidide 16.. a cliloro-l-aminobenzeue l-amii'i'onaphthaleneaA-disulionic z-liygisi-irgirgnaphthaianmarboxylic acid-olied acid an a 17-- 4.0-dichloro-2-amino-1-mathylbenzene i-aminobanzene-2.3-dicarboxylic 2-11ydl'9gildlzphthabn&3-catboXyllc acid- Rad aci p-anisi i l 18.. 4.6-dichloi'o-2-amino-1-metliylbenzene 4-sulio-2-amino-benzoic acid Sodium compound of z-liyd 'oxynaplitha- Rad iene-3-carboxylic acid-camsidrde 19.- 4-chloro-2-aminoi-methylbeuzene Methylamino ethane-sullonic acid Sodium compound oi 2-hydyqxynaphtha- R d lcne-3c.arboxylic acid-o-anisidido 20.. 4-chloi'o-2-amino-l-methoxybenzene Methylamino acetic acid Sodium compound of 2-hydroxynaphtha- Red lene-3-carboxylic acid-oamsidide 21-- 4-chloro-2-amino-1-methylbenzene 4sulfo-2-amino benzoic acid 2-hy di 1 1 apthilialene-Har xylic a id- Red 0- o e 22-- 4-chloro-2-amiuo-1-methylbenzene mulled-amino benzoic acid Sodium compound of 2-hydroxynaplitha- Red Iene-S-carhox; lie and auilido 23.. ,4-niti'o-2 amino-1-metl1oxybenzene 1-methylaminobenzene-4-sulfonic Sodium compound 01 2-hydroxynaphtha- Bluish-red acid lenc-3-carboxyiic acid-m-niti-amlide 24.- 4-amino-1.3-dimethylbenzene l-methyl-Z-ethylamino-benzenewi- 2-11ydi'oxynaplithalene-ii-carboxylic acid-2- Turkey red suifonic acid inetliyl-fl-metiioxyanilidie 25.. 4.lfldichloro-i -amino-l-methylbenzene a-suiioa-amino benzoic acid Sodium compound oi 2-hydroxynaphtha- Turkey red Iene-Ii-carboxylic acid-m-nitranil de 28.. 4.5-dichloro-uamino-l-mcthylbenzene Butylamino-acetic acid 2-hydrp gnpphtlialenc-34arboxyiie acid- Turkey red p-anisi i e 27.- 5-niti'o-2-amino-l-metliylhenzane 4-sulfo-2-aminobenzoic acid Sodium compound 01 -hydlllil'llflphlha- Bordeaux lene-3carboiyiic acid-o-toluididc 28.- 5-nitro-2-amino-1-methy1bcmene 4su.lio-2-amino-benzoic acid 2-hytdi'oiggpiaphthaleue-3-carboiylic acid- Bordeaux oo m i e 29-. o-nitro-z-amino-l-methoxybenzene Cyclolieiylamino-acetic acid Sodium compound of 2-hydi'oxy-na 'lltl lfl- Bordeaux lene-3-carboxylic acid a. naphtl y am de 30.. 3-amino-4-methoxy-6-niti'o-l-methyl- 4-suifo-2-amino-benzoic acid z-liydroxynaplithalene-ti'carboxylic acid- Bordeaux benzene a-naphthylzimido 31.. 3-amino-4-methoxy-6-nitro-i-methyimica-amino benzoic acid Sodium compound of 2-hydroxynaphtha- Bordeaux benzene v Iene-3-carboxylic acid-a-naplithylamide 32.. 3-amino-4-methoxy-6-nitro-1-methyl- Mathylamino acetic acid 2-hydroxynaphthalene-3-carboxyhc acid- Bordeaux benzene fi-n-iphtliyiamide 33.. 3-amino-4-metlioxy-6-niti'o-1-methyli-methylamino-benzene-d sulionic 2-iiydi'o ynaphthaiene-dcarboxylic acid- Bordeaux benzene ac id 2. 5dunetlioxyanilide 34-- fi-nitro-Z-amino-l-methoxybenzene 2ethylamino-l-methylbenzene-4- Sodium compound at z-hydroxynaphtha- Bordeaux sulionic acid lene-ii catboiyiic acid-a-naphthylamide 35-- 3-amino-4-methoxy-e-benzoylamino- Methylamino acetic acid Sodium compound oi 2-li3 droxynaphtha- Violet l-methylbenzene lene-3-carboxyhc acid-anilide 36.- 3amino-4methoxy-6 -benzoyiamino- 1- Cyclohexylamino-acctic acid Sodium compound oi 2-hydroxynaphtha- Violet methylhenzene lene-3-carboiylic acid-o-toiuidida 37-. 3-aniino-4-methoiy-o-benzoylamino- 4-sulio-2-amino-benzoic acid 2-hydi'ou naphthalene-3-earboxy1ic acid- Violet l-znethylbenzene otoluidide 38-- 6-amino-4-benzoylamino-1.3-dimeth- 4-sulio-2-amino-benzoic acid Sodium compound of 2-liydroxynaphtlia- Violet oxybenzen'e lena-3-carboxylic acid-anilide 39.. 6 amino 4 -bcnzoylamino 1.3 di- Butylaminoacetic acid 2-hydroxynaphthalene-ii-carboxylic acid- Violet methoxybenzene o-toluidide 40.. 6 amino 4'- benzoylamino 1.3 di 1-aminobenzene-3.5 dicarboxylic Sodium compound oi 2-hydroxynaphthamethoxy-diphenyl acid lteilieffiirboxyhc acid 5 chloi'o 2 Violet o m i e 41.. 4.4'-diamino-3.3'-dimetlioxybenzene 5-suiio-2-amino-benzoic acid 2-hs dfoiiyp aphthalene-ii-carboxylic acid- Blue oo um. e 42.- o-amiuo-ti-benzoylamino 1.4 di Methyiaminoacetlo acid Sodium compound of 2-hydroxynaphtha- Blue ethoxybenzene lene-li-carboxyhc amd-o-toluididc 43.- fi-ammo-B-benzoylamino 1.4 dicth 4-sulfo-2-amino-benzoic acid 2-hydtoxynaphthalenc 3- carboxylic acid- Blue oxybenzene anilide 44.. 6-amino-3-bcnzoylamino 4 ethoxy Dibonzylamino-di'sulionic acid Sodium compound of Z-hydroxynaphtha- Blue l-methoxybenzene lenes-carbuxylic aczd-0-tolmdidc 45.. G-ammo-B-benzoylamino 4 ethoxy 3-aminobenzenc 1.2 dicai-boxylic Sodium compound of 2-hydroxynaphtlia- Blue l-methoxybenzene ac lene-a-cai'boxyiic ac.d anilide 46.- o-amino-ii-benzoylamino 1.4 di Butylaminoacetlc acid Sodium compound of Z-hydroxynaphtha- Blue m'ethoxybenzene lene-d-cai-boxylic ac 'u-o-toluiuide 47.. 6-amino-3benzoylamino 1.4 di 4-sulio-2-aminobenzoic acid Sodium compound 01 2-hydroxynziplitha- Blue methoxybenzeue lene-li-carboxyiic acid-o-tolliiuluc 48.. 4-cl11oro-2-amjno-1-methylbenzene 4-suiio-2-aminobenzoic acid Sodium compound 01 2-liydi'oxycarnazole- Brown o-cai'boxylio ncid-z toluiuide 49-. 4-mtro-4-amino-2.5'-dimethoxyazo Methylaminoacetic acid Sodium compound 01 Q-iiyuroxyuaphtha- Black benzene lene-z-carboiylic addotoluioide 60.. 3-nitro-4-amino-2'.5- dimethoxyazo Butylaminoacetic acid Sodium compound of 2-hydroxynaphtha- Black benzene lene-li-carboxylic acid-e-naphthyiamidc 51.. 'l-methyl -iamino 2 methoxy 5 Methylaminoethanesulfonic acid Sodium compound of 2-hydroxynaphtha- Black methylazobenzene lcnc-li-carboxylic ac.d-o-toluicice 52.. 4 chloi'o 4' ammo 2 .5 diethoxy 2-methylamino-4-suiiobenzoic acid Sodium compound oi 2-hydroxynaphtha- Black azobenzene lene-Ii-carboxylic acid-a-naphthyiamide We claim:

1. As a new composition of matter a mixture consisting of about equivalent quantities of a coupling component free from sulfonic or carboxylic acid groups suitable for preparing azodyestufl's and a diazo amino compound prepared froma diazotized aromatic amine of the benzene or naphthalene series freefrom sulfonic and carboxylic acid groups and an organic base of the group consisting of primary aromatic and secondary aliphatic and aromatic amines of the benzene or naphthalene series containing at least one of the group consisting of primary aromatic and secondary aliphatic and aromatic amines of the benzene or naphthalene series containing at least one sulfonic or carboxylic acid group, being suitable for dyeing and printin".

g. As a new composition of matter a mixture consisting of about molecular proportions of a 2.3-hydroxynaphthoic acid arylide and a diazo amino compound prepared from a diazotized aminoben'zene which may be sub stituted in the nucleus with the exception of a sulfonic or carboxylic acid group and an organic base of the group consisting of primary aromatic and secondary aliphatic and aromatic amines of the benzene or naphthalene series containing at least one sulfonic or carboxylic acid group, being suitable for dyeing and printing.

4. As a new composition of matter a mixture consistin of about molecular proportions of a 2.3- ydroxynaphthoic acid arylide and a diazo amino compound prepared from diazotized 4-chloro-2-amino-l-methylbenzene and an organic base of the group consisting of primary aromatic and secondary aliphatic and aromatic amines of the benzene. or naphthalene series containing at least one sulfonic or carboxylic acid group, being suitable for dyeing and printing.

5. As a new composition of matter a mixture consisting of about molecular profportions of a coupling component free rom sulfonic or carboxylic acid groups suitable for preparing azodyestuifs and a diazo amino compound prepared from a diazotized aromatic amine of the benzene or naphthalene series free from sulfonic and carboxylic acid groups and a primary aromatic amine of the benzene or naphthalene series substituted by a carboxylic and a sulfonic acid group, being suitable for dyeing and printing.

6. As a new composition of matter a mixture consisting of about equivalent proportions of a 2.3-hydroxynaphthoic acid arylide and a diazo amino compound prepared from a diazotized aromatic amine of the benzene or naphthalene series free from sulfonic and carboxylic acid groups and a primary aromatic amine of the benzene or naphthalene series being substituted by a carboxylic and a sulfonic acid group, being suitable for dyeing and printing. I

7. As a new composition of matter a mixture consisting of about molecular proportions of a 2.3-hydroxyna'phthoic acid arylide and a diazo amino compound prepared from a diazotized aminobenzene which may be substituted in the nucleus with the exception of a sulfonic or carboxylic acid group and a.

, primary aromatic amine of the benzene or naphthalene series being substituted by a carboxylic and a sulfonic acid group, being suitable for dyeing and printing.

8. As a new composition of matter a mixture consisting of. about molecular proportions of a 2.3-hydroxynaphthoic acid arylide and a diazo amino compound prepared from diazotized .t-chloro-2-amino-l-methylbenzene and a primary aromatic amine'of the benzene or naphthalene series which is substituted by a carboxylic and a sulfonic acid group, being suitable for dyeing and printing.

9. As a new composition of matter a mixture consisting of about molecular proportions of 2.3-hydroxynaphthoic acid-o-tolui-' dide and a diazo amino compound prepared from diazotized 4-chloro-2-amino-1-methylbenzene and 4-sulfo-2-a-mino-benzoic acid, being suitable for dyeing and printing.

10. As a new composition of matter a mixture consisting of about equivalent quantities of acoupling component free from sulfonic or carboxylic acid groups suitable for preparing azodyestuifs and a diazo amino compound prepared from a diazotized aromatic amine of the benzene or. naphthalene series free from sulfonic and carboxylic acid groups and an organic base of the group. consisting of secondary aliphatic amines containing at least one sulfonic or carboxylic acid group, being suitable for dyeing and printing.

11. Asa new composition of matter a mixture consisting of about equivalent quantities 'of a.2.3-hydroxynaphthoic acid arylide and a diazo amino compound prepared from adiazotized aromatic amine of the benzene or naphthalene series free from sulfonic and carboxylic acid groups and an organic base of the group consisting of secondary aliphatic amines containing at least one sulfonio or carboxylicacid group, being suitable-for dyeing and printing. I

12. As a new composition of matter a mixture consisting of about-molecular proportions of a 2.3-hydroxynaphthoic acid arylide and a diazo amino compound prepared from a diazotized ammobenzene which may be substituted in the nucleus with the exception of a sulfonic or carboxylic acid group and an organic base of the group consisting of secondary aliphatic amines containing at least one sulfonic or carboxylic acid group, being suitable for dyeing and printing.

13. As a new composition of matter a dry mixture consisting ofabout equivalent quantities of a coupling component free from sulfonic 0r carboxylic acid groups suitable for preparing azodyestufi's and a diazo amino compound prepared from a diazotized aromatic amine of the benzene or naphthalene series free from sulfonic and carboxylic acid groups and an organic base of the group consisting of primary aromatic and secondary aliphatic and aromatic amines of the benzene or naphthalene series containingat least one sulfonic or carboxylic acid group, being suitable for dyeing and printing.

14. As a new composition of matter a dry mixture consisting of about equivalent quantities of a 2.3-hydroxynaphthoic'acid arylide and a diazo amino compound prepared from a diazotized aromatic amine of the benzene or naphthalene series free from sulfonic and carboxylic acid groups and an organic base of the group conslsting of primary aromatic and secondary aliphatic and aromatic amines of the benzene or naphthalene seriescontain- 5 ing at least one sulfonic or carboxylic acid group, being suitable for dyein and printing. 15. As a new composition 0 matter a dry mixture consisting of about molecular proportions of a 2.3-hydroxynaphthoic acid 'arylide and a diazo amino compound prepared from a diazotized amino-benzene which may be substituted in thenucleus with the exception of a sulfonic or carboxylic acid group and an organic base of the group consisting ofv rimary aromatic and secondary aliphatic an aromatic amines of the benzene or naphthalene series containing at least one sulfonic or carboxylic acid group, being suitable for dyeing and printing. 16. As a new composition of matter a dry mixture consisting of about molecular proportions of a coupling component free from sulfonic or carboxylic acid groups suitable for preparing azodyestuifs and a diazo amino compound prepared from a diazotized aromatic amine of the benzene or naphthalene series free from sulfonic and carboxylic acid groups and a primary aromatic amine of the benzene or naphthalene series substituted by a carboxylic and a sulfonic acid group, being suitable for dyeing and printing. 17. As a new composition of matter a dry mixture consisting of about molecular proportions of a 2.3-hydroxynaphthoic acid arylide and a diazo amino compound prepared from diazotized 4-chloro-2-amino-1- methyl-benzene and a primary aromatic amine of the benzene or naphthalene series which is substituted by a carboxylic and a sulfonic acid group, being suitable for dyeing and printing.

18. As a new composition of matter a dry mixture consisting of about molecular roportions of 2.3-hydroxynaphthoic aci -otoluidide and a diazo amino compound prepared from diazotized 4-chloro-2-amino-1- methylbenzene and 4-sulfo-2-amino-benzoic acid, being suitable for dyeing and printing.

In testimony whereof, we afiix our signatures.

J OSEF HALLER. EUGEN GLIETENBERG.

WINFRID HENTRICH. 

